Azodyestuffs and intermediate



Patented Aug. 4, 1936 UNITED STATES PATENT OFFICE AZODYESTUFFS AND INTERMEDIATE PRODUCTS THEREFOR Carl Taube, Leverkusen-I. G.-Werk, and Ernst Tietze, Cologne-on-the-Rhine, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application January 16, 1935, Se-

rial No. 2,116. In Germany January 26, 1934 8 Claims.

The present invention relates to new derivatives of cyanamide carboxylic acid and to the use of the said derivatives for the manufacture of a20- dyestuffs, more particularly it relates to compounds which may be represented by the probable a1 halogenide, when hydrochloric acid is used as acidifying agent, urea and carbon-dioxide, they are valuableproducts for dyeing and printing general formula:

' NEC-NN=N'R c 0 OMe wherein Me stands for a monovalent metallic radical, such as an alkali metal,

bearing at least one substituent which does not cause solubility in water, such as alkyl, alkoxy, halogen, the nitro group, the sulfoneamide group 95 in which the hydrogen atoms may be wholly or partially substituted, for example, by alkyl, aralkyl or aryl, further as substituents there may be present aryloxy, the trifluoromethyl group, .the group SOzR', in which R stands for alkyl, aryl or aralkyl, or a substituted amino group, such as alkylamino, arylamino and acylamino, or an azo group, or R may stand for a polynuclear aromatic radical, such as a radical of the naphthalene, anthraquinone, anthracene and carbazole series,

5 which may bear substituents which do not cause solubility in water.

Our new compounds are obtainable by causing a water-soluble salt of cyanamide carboxylic acid, especially an alkali metal salt thereof, to

40 react with the diazo compound of an aromatic amine of the formula: R-NH2, in which R means the same as stated above, advantageously in an aqueous caustic alkaline to soda alkaline medium and at low temperature.

45 Our new compounds are generally well crystallizing substances, soluble in water, stable at room temperature and also at higher temperatures, say at about 90 C., and insensitive towards percussion.

50 A further step of the invention resides in-the use of our new compounds in the manufacture of azodyestufis in substance or on a substratum, especially the cellulosic fibre; for, due to the fact that on acidifying the new compounds, they are 55 split up into the original diazo compounds, a met- From the equation is to be seen that by acidifying the new stable compounds, there are obtainable diazo solutions ready for being used for dyeing or printing purposes, in which diazo solutions a re-formation of the condensation product from 15 cyanamide carboxylic acid and the diazo compound by neutralization of the acid used as splitting agent cannot enter due to the chemical a1- teration of the cyanamide carboxylic acid.

Further our new compounds can be brought into contact with the coupling components generally used in the manufacture of ice colors in an alkaline medium without a coupling to the azodyestuff occurring. Thus, there can be prepared mixtures from our new compounds and coupling components in which mixtures the two ingredients are favorably present in about equimolecular proportions; if desired, to the dyeing preparations thus obtained wetting and/or dispersing agents may be added. These preparations are especially valuable for printing purposes; they-can be worked into printing color in the usual manner and yield after printing and developing inan acid medium full and clear prints.

For developing the print it is sufficient in some cases to hang the print in the air.

The invention is illustrated by the following examples, without being limited thereto:

" Example 1.16.8 grams of 5-nitro-2-amino-lmethoxybenzene are transformed into the diazo compound with the aid of 6.9 grams of sodium nitrite in hydrochloric acid suspension. The filtered solution is neutralized with sodium bicarbonate and at 5 C. stirred into a, solution of 18 grams of the sodium salt of cyanamide-carboxylic acid (obtainable by reacting upon disodium cyanamide with carbonic acid), in 150 grams of an aqueous sodium carbonate solution of 10% strength. The diazonium salt is quickly consumed, a brownish-yellow precipitate of the triazene being thereby formed, the precipitation of which is completed by the addition of common salt. The precipitate is filtered with suction, washed with aqueous common salt solution and dried in an air stream of -50 C. The condensation product having the following formula:

OCH:

NEC-NN=N OONa is washed with aqueous common salt solution and dried in an air stream of 40-50 C.

In an analogous manner the following diazoamino compounds have been prepared:

8 ozNwnim (")Hr 0 ONE d C H:

C O ONa Gi ls-IS O;

CeHrCHr-S OI ton.

OCH!

N=NN--CEN 6 0 ONa CHNGe-MME. $00K OCH:

, OaN N=NNC EN OONa l OON'a Example 3.About equimolecular quantities ofthe following Diazoamino compounds Coupling components (a) Coupling product from diazotized 5- 2.

nitro-Z-anisidine and the sodium salt of cyanamide-carboxylic acid.

(b) Coupling product from diazotized 5- nitro-Z-tcluidine and the sodium salt of cyanamidecarboxylic acid.

(c) Coupling product from diazotized 4- chloro-Z-anisidine and the potassium salt of c anamide-carboxylic acidv (d) Coup ing product from diazotized 1- amino -4 benzoyl amino 25 dimethoxybenzene and the sodium salt of cyanamide-carboxylic acid.

(e) Coupling product from diazotized 2- aminocarbazole and the potassium salt of cyanamide-carboxylic acid.

3-hydroxynaphthoic acid-a-naphthylamide.

2.3 hydroxynaphthoic acid-o-toluidide.

2.3 hydroxynaphthoic acid-o-anisidide.

Z-hydroxyanthracene 3 uidide.

Diacetoacetic acid-o-tolidide.

are intimately mixed together. these mixtures there may be added stretching agents, such as Glaubers salt, and/or wetting carboxyllc acid o tol- If desired, to r agents, for example, 10% of the sodium salt of ample 1, and 3 grams of 2.3-hydroxy naphthoic ,acid-a-naphthylamide are dissolved with 3.1

grams of highly sulfonated castor oil and 3 grams of caustic soda in 24 grams of water, stirred with 50 grams of starch tragacanth thickener and made up with water to grams. With this printing color cotton tissue is printed, dried in superheated steam containing formic and acetic acid vapors, soaped in a 'boiling bath, rinsed and dried. A full Bordeai'rx of good Iastness properties is thus obtained.

Example 5.-From 2.5 grams of the coupling product from diazotized 5-nitro-2-toluidine and the sodium salt of cyanamide-carboxylic acid and 2.8 grams of 2.3-hydroxynaphthoic acid-o-toluidide a printing color is prepared as described in Example 4. When printed on cotton the same after developing in an acid medium a full clear red of good fastness properties.

Example 7.-From 4 grams of the coupling product from diazotized 2-nitro-4-chloroaniline and the sodium salt of cyanamide-carboxylic acid and 2.8 grams of 2.3-hydroxynaphthoic acid anilide a printing color is prepared as described in Example 4. When printed on cotton the same yields after developing in an acid medium a full yellowish-red. p

In an analogous manner the condensation products from the sodium or potassium salts of cyana mide-carboxylic acid and diazotized 4-nitro-2- toluidine, or 2-nitro-4-toluidine, or 4-ch10r0-2- toluidine, or 2.5-dichloroaniline, or 5-benzoylamino-Z-amino-1.4-diethoxybenzene, or 4-amino- 4'-nitro-3-methoxy-G-methyl-azobenzene, or 2- aminocarbazole or l-aminoanthraquinone yield, when worked into printing pastes with coupling components generally used in the manufacture of ice colors, after printing on cotton and developing in an acid medium, powerful clear shades of good fastness properties.

We claim:

- 1. Compounds of the general formula:

wherein Me stands for an alkali metal atom and R stands for a radical of the benzene series bearing at least one substituent selected from the group consisting of allwl; alkoxy; halogen; the. 'nitro group; the sulfoneamide group, in which drogen atoms of the amino group may be substituted by alkyl, aralkyl or aryi; the trifluoromethyl group; the group SOzR', in which R. stands for alkyl, aryl or aralkyl; aryloxy; a substituted amino group and the azo group. being generally well crystallizing substances, soluble in water and being valuable substances for dyeing and printing purposes. v

2. The compound of the following formula:

60H co'oNa 8 crystallizingin yellow crystals, being soluble in water and being a valuable substance for dyeing and printing purposes.

3. Preparations for dyeing and printing purposes comprising a compound of the general formula as described in claim 1, and a coupling component generally used in the manufacture of ice colors.

4. Preparations for dyeing and printing purposes comprising a compound of the general formula as described in claim 1, and a 2.3-hydroxynaphthoic acid arylamide.

5. Process which comprises applying to cellulosic fibres a compound of the general formula as described in claim 2, and a coupling component generally used in the manufacture of ice colors and developing the dyestufi by treating the cellulosic fibres in anacid medium.

6. Process which comprises applying to cellulosic fibres a compound of the general formula as described in claim 2, and a 2.3-hydroxynaphthoic acid arylamide, and developing the dyestuff by treating the cellulosic fibres in an acid medium.

7. Process which comprises applying to cellulosic fibres a compound of the general formula as described in claim 1, and a coupling component generally used in the manufacture of ice colors and developing the dyestuflf by treating the cellulosic fibres in an acid medium.

8. Process which comprises applying to cellulosic fibres a compound of the general formula as described in claim 1, and a 2.3-hydroxynaphthoic acid arylamide; and developing the dyestufl by treating the cellulosic fibres in an acid medium.

. CARL TAUBE.

ERNST TIE'IZE. 

